Nitrophenylazo-2-hydroxynaphthalene-3-carboxylic acid amine dyestuffs



United States Patent 3,207,748 NITROPHENYLAZO-Z-HYDROXYNAPHTHALENE-3-CARBOXYLEIC ACID AMINE 'DYESTUFFS Werner Bossard and Hans E.Wegmuller, Riehen, near Basel, Switzerland, assignors to J. R. GeigyA.-G.,

Basel, Switzerland No Drawing. Filed Nov. 14, 1962, Ser. No. 237,761Claims priority, application Switzerland, May 30, 1962, 6,580/62 6Claims. (Cl. 260204) The present invention concerns new monoazodyestuffs which are difiiculty soluble in water, processes for theproduction thereof, processes for the dyeing of hydrophobic organicfibres using the new dyestuffs and, as industrial product, the materialdyed with the aid of these dyestuffs.

It has been found that new difliculty water soluble monoazo dyestulfsare obtained by coupling (a) a diazoniurn compound of the benzene serieswhich contains at the benzene nucleus at least one electrophilicsubstituent which does not dissociate acidically in water, at least onesuch substituent being in either 0- or p-position t0 the azo group, with(b) a compound of formula wherein R represents a non-olefinichydrocarbon radical with not more than 8 carbon atoms, i.e. an alkyl,benzyl or phenyl radical which may be further substituted, and Alkylenerepresents a lower alkylene radical with maximally 4 and preferably with2 to 4 carbon atoms,

to form a dyestuif of the general formula 1'10 CO-NH-alkylene-OR (1wherein A represents a phenyl radical which contains at least oneelectrophilic substituent which does not dissociate acidically in water,at least one such substituent being in either 0- or p-position to theazo group, R and alkylene have the meanings given in Formula I, and thecomponents are so chosen that the dyestuff does not contain any watersolubilising groups which dissociate acid in water.

The term electrophilic substituent which does not dissociate acid inwater as used in this specification and the appended claims, of whichsubstituents there are preferably not more than three present in A,means the nitro, cyano and trifiuoromethyl group, the carbalkoxy groupshavings not more than 8 carbon atoms, such as carboxylic acid methyl,ethyl or butyl ester groups, the unsubstituted, monoand disubstitutedcarbamyl groups with maximally 8 carbon atoms; the unsubstituted,monoand disubstituted sulphonic acid amide groups, wherein amide is aradical with not more than 8 carbon atoms, 1 nitrogen atom and 0 to 1oxygen atom, such as sulphonic acid dimethylamide, diethylamide,dibutylamide, phenylmethylamide, piperidide and morpholide groups;phenoxy sulphonyl, methoxyphenoxy sulphonyl and chlorophenoxy sulphonylradicals with maximally 8 carbon atoms; the acyl groups with 2 to 8carbon atoms such as acetyl, propionyl, butyrol, benzoyl groups; thehalogens fluorine, chlorine and bromine.

Further optional substituents compatible with the aforesaidelectrophilic substituent or substituents in the benzene nucleus of Aand designated in this specification as compatible substituents arealkyl with maximally 8 carbon atoms, such as methyl, ethyl, propyl,isopropyl, tert. amyl, isooctyl; cyclohexyl, benzyl, phenyl,methylphenyl, chlorophenyl; alkoxy with maximally 4 carbon atoms such asmethoxy and ethoxy, which may be optionally hydroxylated as, forinstance, in 2-hydroxyethoxy; phenoxy, chlorophenoxy, methylphenoxy;acetylamino, chloroacetylamino, fi-chloropropionylamino, benzoylamino,chlorobenzoylamino, chloromethylsulphonylamino, chlorotriazinylamino andchloropyrimidylamino groups.

Since the dyestuffs are difliculty soluble, as has already been stated,water solubilising groups which dissociate acid in water such as the SOH or the --COOH group are excluded.

Preferably A is a phenyl radical which contains one to two of theaforesaid electrophilic substituents which do not dissociate acid inwater, in the oand p-position to the azo group.

Alkylene in the Formulas I and II represents a lower alkylene radicalwith from 2 to 4 carbon atoms, such as the ethylene, propylene or thebutylene radical.

The term non-olefinic hydrocarbon radical With not more than 8 carbonatoms as used for R in this specification and the appended claims, meansalkyl and chloroalkyl, preferably with not more than 4 carbon atoms, forexample, methyl, ethyl, 2-chloroethyl, propyl; alkoxyalkyl preferablywith not more than 5 carbon atoms such as fi-methoxyethyl or,B-etho-xyethyl; benzyl, methylbenzyl, phenyl or an optionally furthersubstituted phenyl radical, namely, a methylphenyl, chlorophenyl ormethoxyphenyl radical.

Diazonium compounds usable according to the invention are derived, forexample, from the following amines:

l-amino-Z-nitro-benzene, l-amino-2-nitro-4-methylbenzene,1amino-2-nitro-4-methoxybenzene, l-arnino-2-nitro-4-ethoxybenzene,1-amino-2-nitro-4-chlorobenzene, 1-amino-2-nitro-benzene-4-sulphonicacid amide, -rnethylamide, -ethylamide, -dimethylamide, -diethylamide orN-phenyl-N-methylamide, 1-amino-2-nitro-4-trifluoromethylbenzene,l-amino-4-nitrobenzene, 1-amino-4-nitro-2-methylbenzene,1-amino-4-nitro-2-methoxybenzene, 1-amino-4-nitro-2-ethoxybenzene,1-amino-4nitro-2-chlorobenzene, 1-amino-4-nitro-2-bromobenzene,l-amino-4-nitro-2-cyanobenzene, l-amino-4-nitro-2,5-dichlorobenzene,1-amino-4-nitro-2,6-dichlorobenzene, 1-amino-4-nitro-2,G-dibromobenzene,1-amino-4-nitro-3-carboethoxybenzene,1-amino-4-nitro-3-carbobutoxyhenzene,l-amino-2-nitro-4-carbo-diethylamide-benzene,1-amino-2,4-dinitrobenzene, l-amino-2,4-dinitro-6-chlorobenzene,1-arnnno-4-carboethoxybenzene, l-amino-4-carbophenylbenzene,l-amino-2,4-,1-amino-2,5- or l-aminc-3,4-dicyanobenzene,1-amino-2nitro-4-sulphophenoxybenzene,1-amino4-nitro-2-sulfo-2'-methylphenoxy benzene,l-amino-2nitro-4-sulfo-2'chlorophenoxybenzene,1-amino-2-nitro-4-sulfo-3-methoxyphenoxy-benzene,1-amino-2,4-dinitro-6-fluorobenzene.

To produce the preferred dyestuffs in which A is a phenyl radicalelectrophilically substituted in the oand p-position, for example1-amino-2,4-dinitrobenzene and 1-amino-2-cyano-4-nitrobenzene are used.

As azo components of Formula I, condensation products of2-hydroxynaphthalene 3 carboxylic acid and amines of Formula 111 whereinalkylene and R have the meanings given in Formula I are used,

The coupling is performed by the usual methods, advantageously in aweakly acid medium, possibly in the presence of solubility promotorssuch as low aliphatic alcohols, e.g. ethylene glycol monomethyl ormonoethyl ether, or amides of lower fatty acids, in particular dimethylformarnide.

Preferred dyestuffs of the invention correspond to the formula wherein nis an integer ranging from 1 to 2, X is nitro, X is nitro, cyano, chloroor bromo,

X is hydrogen, trifiuoromethyl, alkoxycarbonyl having a 4 total ofmaximally 8 and preferably not more than 5 carbon atoms,N-alkyl-substituted carbamyl with maximally 8 carbon atoms, especiallyN,N-diethyl carbamyl, phenoxysulfonyl, methylphenoxysulfonyl,chlorophenoxysulfionyl, methoxyphenoxysulfonyl, or N-alkyl-substituted,N-phenyl-substituted and N-phenyl-N- alkyl-substituted sulfamyl, all ofsaid sulfamyl radicals having not more than 8 carbon atoms, especiallyN,N-diethylsulfamyl and N-phenyl-N-methyl-sulfamyl,

Z is hydrogen, chloro, bromo or fluoro,

Alkylene is ethylene, propylene or butylene, i.e. an alkylene radicalwith 2 to 4 carbon atoms, especially 1,3-propylene, and

R is a non-olefinic hydrocarbon radical with not more than 8 carbonatoms, which means alkyl and chloroalkyl, preferably with not more than4 carbon atoms, especially methyl, ethyl and chloroethyl; alkoxyalkylwith maximally 8 and preferably with not more than 5 carbon atoms,especially methoxyethyl and ethoxyethyl; benzyl, methylbenzyl, phenyl,methylphenyl, chlorophenyl and methoyxphenyl.

Particularly interesting among these preferred compounds are those ofthe formula wherein 11, X X Z, alkylene and R have the meanings givenunder formula IV.

4- Dyestufis of the invention which are particularly valuable because oftheir excellent drawing power and fastness to light and sublimation arethose of the formulas HCl) O NH-alkyleneO-R N Oz- N=N and Htl) (I) ONH-alkylene-OR l C N (VII) wherein R and alkylene have the meaning givenunder Formula IV.

Compared with the known azo compounds of the phenyl-azo 2hydroxynaphthalene-3-carboxylic acidalkyl, -hydroxyalkyl, -aralkyl,-cycloalkyl, or -arylamide series, the new dyestuffs according to theinvention have a considerably improved drawing power onto polyglycolterephthalate fibres. The dyeings on polyester fibres with compoundsaccording to the invention having two electronegative substituents inthe diazo component, one of GONH alkylene- O R which is a nitro group inp-position to the azo bridge and the other is a nitro or cyano group ino-position to the azo bridge, also differ from dyeings obtained withknown dyestuffs in their considerably increased fastness to light.

0 Polyester fibres dyed with the last-mentioned dyestuffs according tothe invention are distinguished by their excellent drawing power andvery good fastness to rubbing, light and sublimation.

The dyestuffs accordings to the invention are brought into easilydistributable form by milling with dispersion agents. Suitabledispersing agents are, e.g., anionic agents such as alkylarylsulphonates, condensation products of aldehydes, i.e., formaldehyde andnaphthalene sulphonic acids, lignin sulphonates, or non-ionogenic onessuch as fatty alcohol polyglycol ethers. Mixtures of these dispersingagents are used with advantage.

The dyestuffs according to the invention are suitable for the dyeing ofhydrophobic synethic textile fibres from aqueous dispersion, e.g., forthe dyeing of cellulose diand tri-acetate, particularly however, for thedyeing of high molecular esters of aromatic polycarboxylic acids andpolyfunctional alcohols, for example, ethylene glycol terephthalatessuch as Terylene, Dacon," Tergal, Trevira, or Kodel, a high molecularxylenedial terephthalate. The dyestuffs can also be used, however, forthe dyeing of synthetic polyamide fibres such as nylon or of Perlon.

The dyeing of polyesters fibres with aqueous dispersions of dyestuffsaccording to the invention is performed CONH alkylene 0 R advantageouslyat temperatures of over C. under pressure. However, the dyeing can alsobe performed at the boiling point of water in the presence of colourcarriers such as, eg phenylphenol, polychlorobenzene compounds orsimilar auxiliaries.

In individual cases, the drawing power of the dyestuffs If in the aboveexample, the 32.1 parts of 2-hydroxynaphthalene-B-carboxylic acid---phenox.ypropylamide are replaced by 25.9 parts of2-hydroxynaphthalene-3-carboxylic acid-B-ethoxyethylamide or by 33.5parts of 2- can be even improved by mixing two or more of the dye- 5hydroxynaphthalene-3-carboxylic acid-y-benzyloxypropylstuffs accordingto the invention. amide and the coupling is performed under the condi-Depending on the composition of the dyestuffs, yellow tions described,then dyestuffs are obtained which proorange and red dyeings can beattained on polyesters duce scarlet dyeings on polyglycol terephthalatefibres fibres which have very good fastness to rubbing, sublimawhichhave equally good properties. tion and light.

The following examples illustrate the invention. Where EXAMPLE 2 nototherwise stated, parts are given as parts by weight. 5-9 Pa s Of2-hydroxynaphthalene-S-carboxylic acid- The temperatures are in degreescentigrade. The rela- 'y-methoxypropylamide are dissolved in 300 partsby voltionship of parts by weight to parts by volume is as that ume of 1N sodium hydroxide solution and the solution of grammes to cubiccentimetres. is poured, with vigorous stirring, into 60 parts ofconcentrated sulphuric acid, 400 parts of finely crushed ice, EXAMPLE 1200 parts of water and 5 parts of cetyl polyglycol ether.

A fi suspension of 133 parts of 1 i 2 i b The diazonium salt solutionsof 18.3 parts of 1-aminozene in 500 parts of Water, 60 parts of 36%hydrochloric 24'dinit1'0benZem, Produced y dissolving acid and 5 partsof cetyl polyglycol ether are diazotised 2 dinitrobenzene in parts Ofconcentrated sulphuric acid i th usual way at 5 7 b h ddi i f 6 9 partsof and diazotising with the amount of nitrosyl sulphuric acid sodiumnitrite. A solution of 32.1 parts of 2-hydroxy- Corresponding to P511rtsof Sodium nitrite, is added naphthalene-:fl-carboxylic acid.'.-phenoxypro ylamide in dropwise at 0'5O to this fine dispersion. Sodiumacetate 150 parts b volume of 2 N di hydroxide l i is added to thereaction mixture to complete the coupling. and 300 parts of water isadded dropwise to the clear The Scarlet precipitate formed of thecomposition diazonium salt solution so prepared. The mineral acid OHGQNHOH OHZGH OCHa' is then buifered by the addition of sodium acetate.On completion of the coupling, the precipitated dyestuffs of O N @N=N@the formula I p N02 OH CONIIOH;CHCIIO l I is filtered off and washed anddried in the usual way. A N=N preparation produced by milling with acondensation I product of naphthalene-Z-sulphonic acid and formalde- N02 hyde, dyes polyglycol terephthalate fibres such as Tergal(Rhodiaceta, Lyons, France) from an aqueous disis filtered off, Washedwith water, dried in vacuo at 60-70 persion, possibly in the presence ofa carrier such as oand milled with a mixture of a condensation productof phenylphenol, in pure orange shades. The dyeings arenaphthalene-Z-sulphonic acid with formaldehyde and a distinguished by ahigh degree of fastness to light and lignin sulphonate. It is a redpowder which, in aqueous sublimation. dispersion possibly in thepresence of a carrier, dyes p01- The Z-hydroxynaphthalene-3-carboxylicacid-'y-methyglycol terephthalate fibres such as Dacron (E. J. duoxypropylamide used as starting material is obtained in Pont de Nemours,Wilmington, Del., USA.) in pure the usual way by reacting2-hydroxynaphthalene-3-carscarlet shades. The dyeings are fast towashing, rubbing boxylic acid chloride with 'y-methoxypropylamine in theand sublimation. presence of an acid binding agent.

The Z-hydroxynaphthalene-3-carboxylic acid- -phen- Dyestuffs havingsimilar properties are obtained if oxypropylamide is obtained byreacting 2-hydroxynaphequivalent amounts of the diazo and couplingcompothalene-3-carboxylic acid chloride with 'y-phenoxypropylnents givenin the following Table I are coupled under amine. the conditionsdescribed in the above example.

Table I Shade on poly- No. Diazo component Coupling component or mixtureof coupling components ester fibres 1 1-amin0-2-nitro-4-chlorobenzene2-hytllroxynaphthelene-3-carboxylic acid-'y-methoxy-pro- Orange. 2 doz-hgd ib ig iiaphthalene-Ii-carboxylic acid- -(ethoxy- Do.

ethoxy)-propylamide. 3 l-amino-4-nitro-2,fi-dichlorobcnzeneZ-hygrggrggghthalene-3-carboxylic acid-fl-methoxy- Do. 4 do 2-liydfoxynaphthalene-3-earboxy1ie aeid-y-ethoxy-propyh Do. 5 do 2-l iy drgxynaphthalene-3-carboxylic ecid-y-(methoxy- D0.

ethoxy)-propylamide. .6 1-amino-4-nitro-2,5-dichlorobenzene 2-hy}1irgrglpgghthalene-3-carboxylic acid-fl-methoxy- D0. 7 do2-hydioxynaphthalene-l-carboxy1ic aeld-y-(o-methyl- Do.

phenoxy)-propylamide. 8 1-amino-2,4-dinitrobenzene2-hyltllrpgrgggghthalene-marboxylic acid-fi-phenoxy- Do. 9 do 2-ligrd roxynaphthalene-3-carboxylic acid-y-phenoxy- D0.

propylamide. 10 do 2-hydroxynaphthalene-3-carboxylie aeid-fl-propyloxy-D0.

ethylamide. Z-hydroxynaphtha1ene-3-carboxylic acid-'y-methoxyu dopropylanu'de. D0.

- Z-hydroxy-naphthalene-3-carboxyl1c acid-y-phenoxypropylamide. 121-amin02,4-diuitro-6-chl0robenzene Z-hygrgggrggghthalene-3-carboxylicacld-fi-methoxy- Do. 1'; do Z-l iydiioxynaphthalene-carboxylic acid-methoxypropyl Do. 14 rln 24 3 33;ynephthalene-B-carboxylicaeid-B-(methoxy- D0.

cthoxy)-ethylamide.

Table 1Continued Diazo component1-amin0-2-nitro-4-trifiuoromcthylbenzene 171-amino-2-nitrobenzene-4-su1phonie acid diethylamide.

20 1-amino-4-nitro3-carbobutoxybenzene 22 1-amino-2,4-dicyanobenzene1-amino-4-nitro-2-bromo-benzene 1-amiino-2-nitrobenzene-4-carbocylicacid-di-ethylal-amino-2-nitrobenzene-4-sullonic acid-N-phenyl-N-methylami e.

1amino-2,4-dinitr0-6-bromo-benzene 1-arnino-4-nitro-2,G-dibromo-benzenel-amino-Z-nitrob enzeneA-sultonic acid-phenyl-ester1-amino-2-nitrobenzene-t-sulfonie aeid-(2-methylphenyl)-ester.

l-amino-4-nitrobenzene-Z-sulfonic acid-(3-methoxyphenyD-ester.

l-amino-Z-nitro-benzenet-sull'onic acid-(2'-chlorophenyD-ester.

1-amino-2,4-dinitrobenzene l-amino-Z-cyano-et-nitrobenzene EXAMPLE 325.9 parts of 2-hydroxynaphthalene-3-carboxylicacidv-rnethoxypropylamide are dissolved hot in 200 parts of 'dimethylformamide and the solution is poured, while stirring vigorously, into 20parts of concentrated sulphuric acid, 300 parts of finely crushed ice,300 parts of water and 6 parts of cetyl polyglycol ether. The diazoniumsalt solution of 16.3 parts of 1-amino-4-nitro-2- cyanobenzene is addeddropwise at 0-5 to the fine dispersion prepared,whereupon a scarlet redprecipitate is formed. This is filtered off and washed and dried in theusual way. The composition of the dyestutf obtained corresponds to theformula on OIONHCH CH OH O CH3 After milling this dyestutf with acondensation product of naphthalene-(2)-sulphonic acid and formaldehyde,it dyes polyglycol terephthalate fibres such as Trevira (FarbwerkeHoechst, Frankfurt am Main, Germany) from an aqueous dispersion inorange shades which are fast to washing, light and sublimation.

The diazonium salt solution used is produced as follows: 16.3 parts of1amino-4-nitro-2-cyanobenzene are added at 0-5 to 200 parts of a mixtureof concentrated sulphuric acid and nitrosyl sulphuric acid correspondingto 6.9'parts of sodium nitrite. To complete the diazotisation, thereaction mixture is stirred overnight at 05.

Dyestuffs having similarly good properties are obtained if, in the aboveexample, instead of the 25.9 parts of 2-hydroxy-naphthalene-3-carboxy1ic acid-' -methoxypropylamide, 27.3 partsof Z-hydroxynaphth-alene-3-carboxylic acid-v-ethoxypropylamide or 30.3parts of 2-hydroxynaphthalene 3 carboxylicacid-'y-methoxyet-hoxypropylamide are used and coupled with the diazocomponent mentioned under the conditions described.

EXAMPLE 4 2 parts of the dyestuff obtained according to Example 2 aredispersed in 4000 parts of water. 12 parts of the Shade on poly- Couplmgcomponent or mixture of coupling components ester fibresZ-hydroxynaphthalene-3-earboxy1ic acid-y-methoxy- Orange.

propylamide. 2-hydroxynaphthalene-Ii-carboxylic aeid-y-phenoxy- Do.

propylamide. 2-hydroxynaphthaleneB-carboxylic acid-B-phenoxy- Do.

ethylamide. Z-hydrjoxynaphthalene 3-carboxylic acid-y-ethoxy-propyb Do.

ami e. 2-hydroxynaphthalcne3-earboxylic acid-y-benzyloxy- Do.

propylamide. 2-hydroxynaphthalene-B-earboxylie acid-'y-methoxy- Scarletpropylamide. 2-hydroxynaphthalene-3-carboxylic acid-v-(o-methylphen- D0.

oxy)-propylamide. Z-hydroxynaphthalene-3-carboxylic acid-y-methoxy- D0.

propylamide. 2- hydroxynaphthalene-{i-earboxylic aeid-y-(methoxy- D0.

ethoxy)-propy1amide. 2-hydroxynaphthaIene-B-carboxylic acid-y-methoxy-Orange.

ethoxypropylamide. .do Do.

Z-hydroxynaphthalene-S-earboxylic acid-y-methoxy- Do.

propylamide. o Do. 2-hydroxynaphthalene-3-earboxylie acid--yeth0xy-pr0-Do.

py ami e. 2-hydroxynaphthalene-3-carboxy1ic acid-'y-methoxy- Do.

propylamide. do Do.

2-hydroxynapl1thalene-3-carb0xylic acid-y-methoxy- Do.

ethoxypropylamide. 2-hydroxynaphthalene-3-carboxylic acid-'y-phenoxy-D0.

propylamide. do Do. Z-hydroxynaphthaleue-3-carboxylic acid-w-methoxy-Do.

btgsylamide. D n 0.

sodium salt of o-phenylphenol and 12 parts of diammonium phosphate areadded to this dispersion as carrier and 100 parts of polyglycol terephthaliate yarn are dyed for 1 /2 hours at 98. The dyeing is rinsed andaftertreated with dilute sodium hydroxide solution and a dispersingagent.

In this way, an orange dyeing is obtained which is fast to washing,light and sublimation.

If, in the above example, the parts of polyglycol terephtha'late yarnare replaced by 100 parts of cellulose triacetate fabric and dyeing isperformed under the conditions described and afterwards the goods arerinsed with Water, then an orange dyeing is obtained which isdistinguished by a high degree of fastness to washing and sublimation.

EXAMPLE 5 In a pressure dyeing apparatus, 2 parts of the dyestutfobtained according to Example 3 are finely suspended in 2000 parts ofwater which contains 4 .parts of oleyl polyglycol ether. The pH of thedyebath is adjusted to 6-6.5 with acetic acid.

100 parts of polyglycol terephthalate fabric are entered at 50, the bathis heated within 30 minutes to and dyeing is performed for 50 minutes atthis temperature. The dyeing is then rinsed with water, soaped anddried. Under these conditions, an orange dyeing is obtained which isfast to washing, perspiration, light and sublimation.

EXAM'PLE' 6 Polyglycol terephthalate fabric (such as Dacron of E. I. duPont de Nemours, Wilmington, Del., U.S.A.) is impregnated in a foulardat 40 With a liquor of the following composition:

20 parts of the dyestuff obtained according to Ex ample 2 finelydispersed in 7.5 parts of sodium alginate,

20 parts of triethanolamine, 20 parts of octylphenol-polyglycol ether,and 900 parts of water.

The fabric, wrung out to 100% content, is dried at 100 and the dyeing isthen fixed for 30 seconds at a temperature of 210. The dyed goods arerinsed with wherein n is an integer ranging from 1 to 2, X is nitro,

X is a member selected from the group consisting of nitro, cyano, chloroand bromo,

X is a member selected from the group consisting of hydrogen,trifiuonomethyl, lower lalkoky-carbonyl, N- lower alkyl-substitutedcarbamyl, phenoxysulfonyl, methylphenoxysulfonyl, chlorophenoxysulfonyl,methioxyphenoxysulfonyl and N-lower alkyl-substituted, N-phenyl-substituted and N-phenyl-N-lower alkyl-substituted sulfamyl,

Z is a member selected fnom the group consisting of hydro gen, ohloro,br-omo and fiuoro,

alkylene is 'a straight chain alkylene radical with from 2 to 4 carbonatoms, and

R is a member selected from the group consisting of alkyl andchloro'alkyl with maximally 8 carbon atoms, :alleoxyalkyl with maximally8 carbon atoms, benzyl, methylbenzyl, phenyl, methylphenyl, chlorophenyland methoxyphenyl.

2. A compound of the formula H(l) CONHCH2CH2CH2OCH3 l ON 3. A compoundof the formula ([lONHCHzCHzCHzO CH3 alkylene 0 R 4. A compound of theformula Ho ({JONHCH OH CH O-Q N02-ON=N 5. A compound of the formula H0CONHCHZCHZCH2OCH2OH2OCH3 6. A compound of the formula OH(JONHCHBCHZOCHZCHgCHH References Cited by the Examiner UNITED STATESPATENTS CHARLES B. PARKER, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,207,748 September 21, 1965 Werner Bossard et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 10, lines 2 to 7, the right hand side of the formula should readas shown below instead of as in the patent:

HO ONHCH2CH2CH2OCH3 Signed and sealed this 5th day of September 1967.

(SEAL) Attest:

SWIDER EDWARD J. BRENNER Attesting Officer

1. A COMPOUND OF THE FORMULA